Piorko, A., et al. “Nucleophilic Substitution Reactions of η6-O-Dichlorobenzene-η5-Cyclopentadienyliron Hexafluorophosphate”. Section Title: Organometallic and Organometalloidal Compounds, Journal of Organometallic Chemistry, vol. 315, no. 1, 1986, pp. 79-92, https://doi.org/10.1016/0022-328X(86)80413-2.

Genre

  • Journal Article
Contributors
Author: Piorko, A.
Author: Chowdhury, R. L.
Author: Sutherland, R. G.
Author: Abd-El-Aziz, A. S.
Author: Lee, C. C.
Author: Gill, U. S.
Date Issued
1986
Abstract

Reaction of [(η6-o-Cl2C6H4)Fe(η5-C5H5)][PF6] (I) with an excess of PhOH or p-MeC6H4SH in the presence of K2CO3 gave disubstitution of both chloro groups of I, whereas a similar reaction with one equiv of the nucleophile under conditions of high diln. gave monosubstitution of one of the chloro groups of I. Similarly, di- or monosubstitution occurred with PhCH2OH or MeOH as the source of the nucleophile. A reaction occurred between I and o-MeOC6H4NH2 (II), but only the monosubstitution product was obtained, even in the presence of an excess of II. Monosubstitution was obsd. with other nucleophiles contg. the NH2 group, including NH3, NH2NH2, MeNH2 and PhCH2NH2. Reaction between I and the carbanion-enolate anion derived from acetylacetone, α-benzoylacetophenone, diethyl malonate or ethyl acetoacetate gave monosubstitution of one of the chloro groups leading to the formation of a C-C bond. An explanation for formation of monosubstitution products in reactions with N- or C-contg. nucleophiles was discussed. [on SciFinder(R)]

Note

Dep. Chem., Univ. Saskatchewan, Saskatoon, SK, Can.

Copyright (C) 2012 American Chemical Society (ACS). All Rights Reserved.; Section Code: 29-12; CODEN: JORCAI; CAS Registry Numbers: 77487-02-6 Role: RCT (Reactant), RACT (Reactant or reagent) (nucleophilic substitution reactions of); 108663-29-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and reaction of, with sodium amide); 77487-04-8P; 108663-13-4P; 108663-15-6P; 108663-17-8P; 108663-19-0P; 108663-21-4P; 108663-23-6P; 108663-25-8P; 108663-27-0P; 108663-30-5P; 108663-32-7P; 108663-34-9P; 108663-36-1P; 108663-38-3P; 108663-40-7P; 108663-42-9P; 108935-82-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 90-04-0 (o-Anisidine); 100-51-6 (Benzyl alcohol); 105-53-3 (Diethyl malonate); 106-45-6 (p-Thiocresol); 108-95-2 (Phenol); 120-46-7; 123-54-6 (Acetylacetone); 141-97-9 (Ethyl acetoacetate) Role: RCT (Reactant), RACT (Reactant or reagent) (substitution reaction of, with (dichlorobenzene)iron complex)

Source type: Electronic(1)

Language

  • English

Subjects

  • nucleophilic
  • substitution
  • iron
  • carbanion
  • chlorobenzene
  • enolate
  • ANION
  • Substitution reaction (of (dichlorobenzene)(cyclopentadienyl)iron hexafluorophosphate)
  • chlorobenzeneiron
Page range
79-92
Host Title
Section Title: Organometallic and Organometalloidal Compounds
Journal of Organometallic Chemistry
Host Abbreviated Title
J. Organomet. Chem.
Volume
315
Issue
1
ISSN
0022-328X
DOI
https://doi.org/10.1016/0022-328X(86)80413-2

Department